Ammonia-based desulfurization process and apparatus

ABSTRACT

Apparatus and methods for desulfurization of a sulfur-oxide containing gas by treatment with ammonia containing liquids. The apparatus and methods may utilize two distinct circuits of two different ammonia containing liquids which are applied in two distinct chambers. The gas may be cooled prior to entry into the circuits. There may be fluid communication between the two circulation circuits.

This application is a continuation of U.S. application Ser. No.16/357,831, filed on Mar. 19, 2019, which claims benefit of U.S.application Ser. No. 16/188,816, filed on Nov. 13, 2018, which claimsthe benefit of U.S. application Ser. No. 16/018,386, filed on Jun. 26,2018, which claims the benefit of U.S. application Ser. No. 15/619,122,filed on Jun. 9, 2017, which claims priority under 35 U.S.C. § 119 ofChinese Patent Application No. 201710379460.3, filed on May 25, 2017,all of which are hereby incorporated herein in their entireties.

TECHNICAL FIELD

This disclosure relates to compositions, methods, and apparatuses forremoving sulfur dioxide from exhaust gases. More specifically, thisdisclosure pertains to the use of separate chambers applying differentforms of ammonia to remove sulfur dioxide from exhaust gases.

BACKGROUND

It has long been a desire to remove sulfur dioxide from exhaust gases.One widely used method of removing sulfur dioxide is limestonedesulfurization. Unfortunately, limestone desulfurization processesproduce massive quantities of unwanted waste water and gypsum slag whosetreatment requires onerous investment.

In addition, in the limestone desulfurization process, for every 1 tonof sulfur dioxide removed, about 0.7 ton of carbon dioxide isconcurrently produced.

An alternative method of desulfurization is ammonia-based. Ammonia-baseddesulfurization produces virtually no waste water or waste slag andproduces a useful byproduct, ammonium sulfate fertilizer. Thus, it ismore economic and environmentally friendly.

Chinese patents CN 1283346C and CN 1321723C disclose a process forremoving SO₂ from coal-fired flue gas by using ammonia as a removalagent. These patents describe reducing SO₂ concentration in the exhaustto levels as low as 100mg/Nm³. The process they describe results insignificant amounts of ammonia escaping from the exhaust, sometimes ashigh as 12 mg/Nm³.

Chinese Patent CN 100428979C discloses an ammonia-based desulfurizationprocess using a multi-section structure, including an oxidation section,a crystallization section, a cooling absorption section, a mainabsorption section, and a dehydration-demisting section from bottom totop.

Chinese Patent CN 103301705B discloses an apparatus and a process forcontrolling fine particulate matters in desulfurized flue gas. Itincludes an absorption liquid demister for removing most of the dropletslarger than 10 p.m, a flue gas demister for removing fine particulatematters by rewashing, and a water scrubbing process downstream from theabsorption section. It describes achieving no less than 60% removal rateof fine particulate matters.

However, there is still a need for an ammonia-based desulfurizationprocess which achieves adequate desulfurization of exhaust gases whilesimultaneously inhibiting ammonia escape and aerosol formation.

BRIEF DESCRIPTION OF THE DRAWINGS

The objects and advantages of the invention will be apparent uponconsideration of the following detailed description, taken inconjunction with the accompanying drawings, in which like referencecharacters refer to like parts throughout, and in which:

FIG. 1 illustrates a schematic representation of an ammonia-mixingchamber and an oxidation chamber in accordance with the principles ofthe invention.

FIG. 2 illustrates a schematic representation of a gas desulfurizationapparatus in accordance with the principles of the invention.

FIG. 3 illustrates a schematic representation of a detailed close-upview of an ammonia-mixing chamber and an oxidation chamber in accordancewith the principles of the invention.

For the purposes of this disclosure, like reference numerals in thefigures shall refer to like features unless otherwise indicated. Thedrawings are only exemplifications of the principles of the inventionand are not intended to limit the invention to the particularembodiments illustrated.

DETAILED DESCRIPTION

Definitions

“Ammonia-containing liquid” means a liquid including at least oneammonia or amine based compound, including for example, ammonium salts,ammonium ions (NH4+), ammonium sulfate, ammonium sulfite, and anycombination thereof. The liquid may be water.

“Ammonification” means a chemical treatment utilizing ammonia or anammonia containing compound, it includes but is not limited to sprayingan ammonia bearing liquid into a gas.

“Ammonia-mixing chamber” means a chamber in which an ammonia containingmaterial is prepared, for purposes of this application, the terms“Ammonia-mixing chamber” and “Ammonia-Mixing Chamber” are used hereininterchangeably.

“Absorbent” means a first material, such as an ammonia containingmaterial, whose use in a treatment process can remove a targetedmaterial, such as sulfur dioxide, from a second material, such as gas,flue gas, or exhaust gas.

“Dust” means a particulate material fine enough to waft along gaseousflows, when handled, processed, or contacted. It includes but is notlimited to aerosols, including solid aerosol particles and liquidaerosol particles, soot, charcoal, non-combusted coal, fine minerals,sand, gravel, salts, and any combination thereof.

“Exhaust” means a flow of gas exiting an industrial or chemical process.It includes but is not limited to flue gas, tail gas, exhaust gases fromovens, furnaces, boilers, and/or generators. It may include combustionproducts derived from the combustion of air and flammable material,residual material from chemical processes, which may include water,nitrogen, and pollutants, such as particulate matter, soot, carbonmonoxide, nitrogen oxides, and sulfur oxides. The exhaust of one processmay be a gaseous input to another process.

“Oxidation Rate” means the percentage, calculated by mol percent, of agiven material that has been converted into an identified more-oxidizedspecies of the material. For example, in a mixture containing ammoniabearing species and sulfur oxides, if X mol % of the mixture is ammoniumsulfate, Y mol % is ammonium sulfite or ammonium bisulfite, and Z mol %is some other ammonia, sulfur, and/or oxygen containing species with anoxidation potential greater than ammonium sulfate, because ammoniumsulfate is the identified most-oxidized species, the oxidation rate ofthe mixture would be X mol %.

In the event that the above definitions or a description statedelsewhere in this application is inconsistent with a meaning (explicitor implicit) that is commonly used, set forth in a dictionary, or statedin a source incorporated by reference into this application, theapplication and the claim terms in particular are understood to beconstrued according to the definition or description in thisapplication, and not according to the common definition, dictionarydefinition, or the definition that was incorporated by reference. In theevent that a claim term can only be understood if it is construed by adictionary, a definition set forth in the Kirk-Othmer Encyclopedia ofChemical Technology, 5th Edition, 2005, (John Wiley& Sons, Inc.) shallcontrol, if provided therein.

Apparatus and methods of ammonia-based oxidative desulfurization areprovided.

The apparatus and methods may help meet discharge requirements. Underthe conditions that the SO₂ concentration in the original flue gas isnot more than 30000 mg/Nm³, and the concentration of total particulatematters is not more than 30 mg/Nm³, in the post-treatment clean fluegas, the SO₂ content may reach no more than 35 mg/Nm³ and the total dust(including aerosols) content no more than 5 mg/Nm³.

Using the apparatus and methods, the free ammonia content inpost-treatment clean flue gas may not be more than 3 mg/Nm³, and theutilization rate of ammonia may reach up to 99% or more. The apparatusand methods may help achieve a high purification efficiency, operatestably and reliably, and reduce secondary pollution.

At least one embodiment is directed toward an apparatus and methods forremoving sulfur dioxide from exhaust gas.

The methods may include directing a current of sulfur dioxide containinggas through a vessel. A step of the methods may be mixing, in anammonia-mixing chamber, a liquid and an ammonia source to produce afirst ammonia-containing liquid that has a first pH. Another step of themethods may be contacting, in an oxidation chamber, an oxygen-containinggas with a second ammonia-containing liquid that has a second pH that islower than the first pH. Another step of the methods may be spraying thefirst ammonia-containing liquid in the vessel against the current. Afterspraying the first ammonia-containing liquid, a further step may berecirculating the first ammonia-containing liquid to the ammonia-mixingchamber. Another step of the methods may be spraying the secondammonia-containing liquid in the vessel against the current. Afterspraying the second ammonia-containing liquid, a further step may berecirculating the second ammonia-containing liquid to the oxidationchamber.

The methods may include a transferring of material (mass transfer)between the oxidation chamber and the ammonia-mixing chamber through abalance hole set in a partition between the oxidation chamber and theammonia-mixing chamber. A balance hole may provide for mass transferbetween two different chambers.

The transferring may occur at a location in a top surface of theammonia-mixing chamber. The transferring may occur at a location in alower third of a height of the ammonia-mixing chamber.

The transferring may include transferring through a balance hole that isno more than 0.25 m². The transferring may include transferring througha balance hole that is no more than 0.1 m². The transferring may includetransferring through a balance hole that is no more than 0.05 m². Thetransferring may include transferring through a balance hole that is nomore than 0.01 m². The transferring may include transferring through abalance hole of any suitable size.

The transferring may include transferring through a balance hole that isround. The transferring may include transferring through a balance holethat is rectangular. The transferring may include transferring through abalance hole that is square. The transferring may include transferringthrough a balance hole that is oval. The transferring may includetransferring through a balance hole that is hexagonal. The transferringmay include transferring through a balance hole of any suitable shape.

The mixing may include receiving ammonia in the ammonia-mixing chamber,at a material transfer port disposed in a surface of the ammonia-mixingchamber. The material transfer port may be distant from the balancehole. The spraying of the first ammonia-containing liquid may includedrawing the first ammonia-containing liquid from the ammonia-mixingchamber. The material transfer port may be in fluid communication withan elongated conduit leading away from the ammonia-mixing chamber.

The mixing may include receiving ammonia in the ammonia-mixing chamber,at a first side of the ammonia-mixing chamber. The spraying of the firstammonia-containing liquid may include drawing the firstammonia-containing liquid from the first side. The transferring ofmaterial may include transferring material through a balance hole set ina second side of the ammonia-mixing chamber. The first side may belocated away from the second side.

The methods may include, before spraying the first ammonia-containingliquid in the vessel against the current, cooling the current bycontacting it with ammonium sulfate slurry. The methods may include,before spraying the first ammonia-containing liquid in the vesselagainst the current, cooling the current by contacting it withammonia-containing liquid. The ammonia-containing liquid may includerecirculated sprayed ammonia-containing liquid.

When directed into the vessel for treatment by the process, the incomingsulfur dioxide containing gas may have a concentration of sulfur dioxideof more than 28,000 mg/Nm³. The incoming gas may have a concentration ofsulfur dioxide of not more than 30,000 mg/Nm³. The incoming sulfurdioxide containing gas directed into the vessel for the treatment mayhave a total particulate matter concentration of more than 25 mg/Nm³.The incoming gas may have a total particulate matter concentration ofnot more than 30 mg/Nm³.

The methods may include releasing (exhausting) the gas current from thevessel after the treatment. When released, the exhausted gas may have aconcentration of sulfur dioxide of not more than 30 mg/Nm³. Theexhausted gas may have a concentration of sulfur dioxide of not morethan 35 mg/Nm³. When released, the exhausted gas may have a total dustcontent (including aerosols) of not more than 5 mg/Nm³.

The methods may include receiving the gas current from a coal combustionprocess. The methods may include receiving the gas current from afluidized bed catalytic cracking process.

The ammonia source may include anhydrous ammonia. The ammonia source mayinclude gaseous ammonia. The ammonia source may include aqueous ammonia.

The methods may include, after spraying the first ammonia-containingliquid and the second ammonia-containing liquid, mixing the first andsecond ammonia-containing liquids to form a mixed reflux liquid.

The methods may include circulating reflux liquid into theammonia-mixing chamber. The methods may include passing between 30% and85% of the reflux liquid into the ammonia-mixing chamber.

The methods may include circulating reflux liquid into the oxidationchamber. The methods may include passing between 15% and 70% of thereflux liquid into the oxidation chamber.

The methods may include contacting anhydrous ammonia with the refluxliquid via a microporous distributor and adding the resulting mixtureinto the ammonia-mixing chamber.

The oxygen-containing gas may include pure molecular oxygen. Theoxygen-containing gas may include oxygen-poor air. The oxygen-containinggas may include oxygen-enriched air.

The methods may include, prior to the mixing of the liquid and theammonia source in the ammonia-mixing chamber, mixing the ammonia sourcewith the oxygen-containing gas.

The oxidation rate of the first ammonia-containing liquid within theammonia-mixing chamber may be in the range 93% to 99.5%. The oxidationrate of the first ammonia-containing liquid within the ammonia-mixingchamber may be greater than or equal to 98.5%. The oxidation rate of thefirst ammonia-containing liquid within the ammonia-mixing chamber may bein the range 98.5% to 99.5%.

The oxidation rate of the second ammonia-containing liquid within theoxidation chamber may be greater than or equal to 98.5%. The pH of thesecond ammonia-containing liquid may be in the range 4.0 to 6.8.

The methods may include, prior to spraying the first ammonia-containingliquid, mixing the ammonia source with the first ammonia-containingliquid.

The methods may include, after the spraying of the firstammonia-containing liquid and the spraying of the secondammonia-containing liquid, mixing the first and secondammonia-containing liquids to form a mixed reflux liquid. Before asubsequent spraying of the first ammonia-containing liquid in the vesselagainst the current, the methods may include cooling the current bycontacting the current with the recirculated sprayed ammonia-containingliquid. Before a subsequent spraying of the second ammonia-containingliquid in the vessel against the current, the methods may includecooling the current by contacting the current with the recirculatedsprayed ammonia-containing liquid.

The methods may include releasing the gas current from the vessel,wherein the released gas current may have an entrained ammonia amount ofless than or equal to 35 mg/Nm³. When released, the exhausted gas mayhave an entrained ammonia amount of not more than 3 mg/Nm³.

The methods may include adjusting one or both of the pH of the liquidwithin the oxidation chamber and the pH of the liquid within theammonia-mixing chamber by adjusting an opening therebetween. The openingmay control a fluid communication between a first conduit carrying thefirst ammonia-containing liquid and a second conduit carrying the secondammonia-containing liquid. The opening may be adjusted via a sealablevalve in the opening.

The methods may include the ammonia-mixing chamber disposed separatelyfrom the oxidation chamber. The oxidation chamber and the ammonia-mixingchamber may be in fluid communication via a conduit extending betweenthe oxidation chamber and the ammonia-mixing chamber.

The methods may include the ammonia-mixing chamber disposed within theoxidation chamber. The ammonia-mixing chamber may be disposed at leastpartly within the oxidation chamber.

The methods may include the spraying the first ammonia-containing liquidin the vessel against the current sequentially before the spraying thesecond ammonia-containing liquid in the vessel against the current.

The apparatus may include a first sprayer circuit configured to spray afirst liquid countercurrent to a gas stream. The apparatus may include asecond sprayer circuit configured to spray a second liquidcountercurrent to the gas stream.

The first sprayer circuit may include a first sprayer assembly and anammonia-mixing chamber. The ammonia-mixing chamber may include anammonia input port. The ammonia-mixing chamber may include a liquidinput port. The ammonia-mixing chamber may include a first-liquid returnport. The first-liquid return port may be configured to receive thefirst liquid after the first liquid is sprayed. The ammonia-mixing mayinclude a first-liquid supply port. The first-liquid supply port may beconfigured to supply the first liquid to the first sprayer assembly.

The second sprayer circuit may include a second sprayer assembly and anoxidation chamber. The second sprayer assembly may be locateddownstream, relative to the gas stream, from the first sprayer assembly.The oxidation chamber may include a gas input configured for contactingan oxygen-containing gas with an ammonia-containing liquid in theoxidation chamber. The ammonia-containing liquid may be a slurry. Theoxidation chamber may include a second-liquid return port. Thesecond-liquid return port may be configured to receive the second liquidafter the second liquid is sprayed. The oxidation chamber may include asecond-liquid supply port. The second-liquid supply port may beconfigured to supply the second liquid to the second sprayer assembly.

The ammonia-mixing chamber may define a balance hole. The balance holemay place material from inside the ammonia-mixing chamber in diffusivecommunication with material from outside the ammonia-mixing chamber. Thebalance hole may place in diffusive communication a first effluent ofthe first-liquid return port and a second effluent of the second-liquidreturn port.

The oxidation chamber may include a spray array in communication withthe first-liquid return port and the second-liquid return port.

The apparatus may include a conduit configured to transfer the firstliquid from the first-liquid return port to the ammonia-mixing chamber.

The apparatus may include a cooling chamber in which the gas stream iscooled by contacting the gas stream with recirculated sprayedammonia-containing liquid, before spraying the first liquidcountercurrent to the gas stream. An internal volume of the oxidationchamber may partly overlap an internal volume of the cooling chamber.

The apparatus may include a conduit having a first end and a second end.The first end may be configured to be joined to a primary sprayabsorption section upstream from the first spray assembly. The secondend may be bifurcated. The second end may be configured to be joined tothe oxidation chamber and to be joined to the ammonia-mixing chamber.

The apparatus may include a gas cap configured to transfer the gasstream from the first sprayer assembly to the second sprayer assembly.

The apparatus may include a sealable valve. The valve may be configuredto adjust fluid communication between a first conduit carrying the firstliquid from the first-liquid supply port and a second conduit carryingthe second liquid from the second-liquid supply port.

The ammonia-mixing chamber may have a volume no less than a volume ofthe first liquid that is supplied to the first sprayer array over aperiod of two minutes.

The ammonia-mixing chamber may be disposed at least partly within theoxidation chamber. The ammonia-mixing chamber may be located within theoxidation chamber.

The ammonia-mixing chamber may include a first side and a second side.The ammonia input port may be positioned along the first side. Theliquid input port may be positioned along the first side. Thesecond-liquid return port may be positioned along the first side. Thebalance hole may be positioned along the second side. The balance holemay be at least one balance hole. The balance hole may be one or morethan one balance hole.

The ammonia-mixing chamber may include a surface that defines thebalance hole. The ammonia-mixing chamber may include a top that definesthe balance hole. The balance hole may be disposed in a lower third of aheight of the ammonia-mixing chamber.

The balance hole may be no more than 0.25 m². The balance hole may be nomore than 0.1 m². The balance hole may be no more than 0.05 m². Thebalance hole may be no more than 0.01 m².

The balance hole may be round. The balance hole may be rectangular. Thebalance hole may be square. The balance hole may be oval. The balancehole may be hexagonal.

The ammonia-mixing chamber may include a material transfer port that isdisposed in a surface of the mixing chamber. The material transfer portmay be in fluid communication with an elongated conduit leading awayfrom the mixing chamber.

The material transfer port may be distant from the balance hole. Thematerial transfer port may be a distant port. The distant port may be aport closer to the balance hole than any other material transfer port inthe mixing chamber. The other material transfer port(s) may be in fluidcommunication with one or more than one other elongated conduit leadingaway from the mixing chamber.

The ammonia-mixing chamber may have a first cross-sectional area, theoxidation chamber may have a second cross-sectional area, and the secondcross-sectional area may be larger than the first cross-sectional area.

The first cross-sectional area may be about 75% of the secondcross-sectional area. The first cross-sectional area may be about 85% ofthe second cross-sectional area. The first cross-sectional area may beno more than 60% of the second cross-sectional area. The firstcross-sectional area may be no more than 50% of the secondcross-sectional area. The first cross-sectional area may be no more than40% of the second cross-sectional area.

The first cross-sectional area may be within the range 8-50% of thesecond cross-sectional area. The first cross-sectional area may bewithin the range 8-40% of the second cross-sectional area. The firstcross-sectional area may be within the range 10-35% of the secondcross-sectional area.

The apparatus may include a conduit configured to transfer the firstliquid from the first-liquid return port to the cooling chamber. Theapparatus may include a conduit configured to transfer the second liquidfrom the second-liquid return port to the cooling chamber.

The balance hole may be disposed in a partition between the oxidationchamber and the ammonia-mixing chamber. The oxidation chamber and theammonia-mixing chamber may be in fluid communication via the balancehole.

A conduit may extend between the oxidation chamber and theammonia-mixing chamber. The oxidation chamber and the ammonia-mixingchamber may be in fluid communication via the conduit.

The methods may include a process. The process may include a number ofsteps. A sulfur dioxide-containing gas to be treated is provided. The tobe treated gas is fed into an oxidation chamber. Another gas containingoxygen and a reflux liquid are also fed into the oxidation chamber. Theoxygen containing gas is bubbled through a liquid phase in the oxidationchamber. Another portion of the reflux liquid and an ammonia absorbentare fed into an ammonia-adding chamber while maintaining a fluidconnection between the ammonia-adding chamber and the oxidation chamber.At least one part of a liquid stream taken from the lower portion of theoxidation chamber as a second spray wash liquid is fed into a secondspray wash section. At least one part of a liquid stream taken from thelower portion of the oxidation chamber is fed into a subsequent unit torecover ammonium sulfate. The liquid stream taken from the lower portionof the ammonia-adding chamber is fed as the first spray wash liquid intothe first spray wash section. The gaseous stream from the oxidationchamber may optionally be separated by the gas-liquid separator. Thegaseous stream is fed into a cooled concentration section in which theto be treated gas stream is cooled by being brought into indirectcontact with the coolant. The to be treated gaseous stream then passesfrom the cooled concentration section into the first spray wash sectionwhere it undergoes countercurrent contact with the first spray washliquid. The to be treated gaseous stream then passes to the second spraywash section where it undergoes countercurrent contact with the secondspray wash liquid. The liquids from the bottom of the first spray washsection and the bottom of the second spray wash section, are fed eitherseparately or after being mixed together, into one or bothammonia-adding chamber and the oxidation chamber. The now treated gas isemptied out of the second spray wash section.

The sulfur dioxide-containing gas to be treated may be a flue gasproduced by coal combustion.

The sulfur dioxide-containing gas to be treated may be a flue gasproduced in a fluid catalytic cracking process.

The ammonia absorbent may be in the form of liquid ammonia, gaseousammonia, ammonia water, or their combination.

The oxygen-containing gas may be oxygen, air, or oxygen-enriched air.

The ammonia absorbent may be added to the liquid stream using a tubulardistributor, a microporous distributor, or a static mixer, and theammonia absorbent may be first mixed with the oxygen-containing air andthen the mixed gas stream may be directly added into the ammonia-addingchamber.

The pH of the circulating fluid taken from the lower portion of theammonia-adding chamber may be in the range 4.6-8.0.

In at least one embodiment of the process, no ammonia absorbent may beadded into the oxidation chamber other than the ammonia absorbent fromthe reflux liquid and ammonia absorbent from the ammonia-adding chamber.

The oxidation rate in the ammonia-adding chamber may be in the range 93%to 99.5%.

The oxidation rate in the oxidation chamber may be no less than 98.5%.

A calculation of the total reflux liquid may be based on the refluxliquid from the first absorption spray section and the second absorptionspray section, and 30%-85% of the reflux liquid enters theammonia-adding chamber while the rest of the reflux liquid enters theoxidation chamber.

A valve may be provided between the pipe to take out the circulatingliquid from the lower portion of the oxidation chamber and the pipe totake out of the circulating liquid from the lower question of theammonia-adding chamber to allow adjustment to the amount of circulatingliquid that respectively enters the first spray wash section and thesecond spray wash section.

The spray liquid from the bottom of the first spray wash section and thesecond spray wash section may be combined and refluxed, wherein about 60to about 70% of the reflux liquid may be combined with the ammoniaabsorbent to enter the ammonia-adding chamber, and the remainder of thereflux liquid may enter the oxidation chamber.

A portion of the ammonia absorbent may enter the portion of the refluxliquid to be fed to the ammonia-adding chamber through the microporousdistributor and may be added into the ammonia-adding chamber after it ismixed with the other part of the ammonia absorbent and theoxygen-containing gas.

The ammonia absorbent may be further added to at least one of the cooledconcentration section, the first spray wash section, and the secondspray wash section.

The condition of the SO₂ concentration of the original flue gas may beno more than 30,000 mg/Nm³, the total particulate matter concentrationis no more than 30 mg/Nm³, the total particulate matter includingaerosol is ≤5 mg/Nm³, and the amount of the entrained ammonia is no morethan 3 mg/Nm³.

The apparatus may include an oxidative absorption section, a cooledconcentration section, a first spray wash section, and a second spraywash section. The oxidative absorption section may include an oxidationchamber. The oxidation chamber may be configured to allow the contactand reaction of a gaseous stream with a liquid phase. The gaseous streamenters from chamber's bottom, allowing the bubbling of the gaseousstream through the liquid phase in the bottom of the oxidation chamber.After passing through the liquid phase, the gas may undergo a gas-liquidseparation process and then enter the upper portion of the cooledconcentration section. At least a portion of the liquid phase may befrom a liquid stream to be taken from the bottom of a spray washsection. The oxidative absorption section may also include anammonia-adding chamber. The ammonia-adding chamber may be configured tohave a fluid connection with the oxidation chamber. The connection maybe located on the top or the sides of the ammonia-adding chamber. Theconnection allows reflux liquid to enter from its upper portion andallow the removal of a liquid stream from its lower portions. The cooledconcentration section may be configured to allow the indirect contact ofa gaseous stream that enters the cooled concentration section with acoolant from the oxidation section. The cooled gaseous stream may thenenter the first spray wash section. The gas may enter the spray washsection through a partition with a gas cap. The first spray wash sectionmay be configured to allow countercurrent contact between the gaseousstream and sprayed liquid that enters the first spray wash section fromits upper portion. After spraying, the spray liquid may be taken outfrom a lower portion of the first spray wash section to provide refluxliquid. The gaseous stream then passes on to the second spray washsection. The gaseous stream may enter the second spray wash section bypassing through a petition with a gas cap. The second spray wash sectionmay be configured to allow countercurrent contact between the gaseousstream and a spray liquid. The spray liquid may enter the second spraywash section from its upper portion. After being sprayed, the sprayliquid may provide reflux liquid.

The oxidation chamber may be set up inside an absorption tower. Theammonia-adding chamber may be set up either inside the absorption toweror outside the absorption tower. Alternatively, both the oxidationchamber and the ammonia-adding chamber may be set up inside theabsorption tower and may be formed by a section of separation in thelower portion of the absorption tower. The volume of the ammonia-addingchamber may be not less than the amount of the liquid taken out from thelower portion of the oxidation chamber in 2 minutes.

A valve may be provided between the pipe to take out the circulatingliquid from the lower portion of the oxidation chamber and the pipe totake out of the circulating liquid from the lower question of theammonia-adding chamber to allow adjustment of the amount of circulatingliquid that respectively enters the first spray wash section and thesecond spray wash section.

The oxidation chamber and the ammonia-adding chamber may be set upinside an absorption tower and may be formed by a section of separationin the lower portion of the absorption tower.

The maximum cross-sectional area in the absorption tower occupied by thecross-sectional area of the ammonia-adding chamber may be 85%, or nomore than 60%, or no more than 50%, or no more than 40%, or in the range5-50%, or in the range 7-40%, or in the range 10-35%.

The sides and/or top of the ammonia-adding chamber may have an opening.

The ammonia-adding chamber may have one or more balance holes in thelower ⅓ of the side.

The ammonia-adding chamber may have one or more openings in the roof

The area of the opening in the ammonia-adding chamber may be no morethan 0.25 m², or no more than 0.1 m², or no more than 0.05 m², or nomore than 0.01 m^(2.)

The opening of the ammonia-adding chamber may be round, rectangular,square, oval, or hexagonal.

The balance holes on the sides and/or the top of the ammonia-addingchamber may be located away from all the inlets and outlets of thematerials.

The apparatus may include having no spacer between the oxidizing sectionand the cooled concentration section. There may be a spacer between theoxidizing section and the cooled concentration section that allows thegaseous substance to pass through smoothly.

Embodiments

In the apparatus and methods, an ammonia-based desulfurization processin which the sulfur absorption may occur in different chambers. Anoxidation section may include an oxidation chamber and an ammonia-mixingchamber in fluid communication with each other. An ammonia absorbent maybe added to the ammonia-mixing chamber. Liquids and gases may be fed ormoved between the various chambers and sections via one or moreconduits.

In some embodiments, the absorption-oxidation cycle of the ammonia-baseddesulfurization process may include liquid circulation circuit betweenthe oxidation chamber and a secondary spray absorption section. It alsomay include a liquid circulation circuit between the ammonia-mixingchamber and a primary spray absorption section. There may be a partialfluid communication between the two circulations circuits. This partialfluid communication may occur via one or more connections between theoxidation chamber and the ammonia-mixing chamber.

In some embodiments, the ammonia-based desulfurization process mayinclude providing a sulfur dioxide-containing gas stream to be treated.

The process may include feeding the sulfur dioxide-containing gas streamto be treated into a cooling concentration section, where the gas streammay be washed and cooled using a circulating washing liquid in thecooling concentration section while concentrating the circulatingwashing liquid in the cooling concentration section using the heat inthe gas stream.

The process may include allowing the gas stream from the coolingconcentration section to enter the primary spray absorption section,where the gas stream may be in countercurrent contact with a first sprayabsorption liquid.

The process may include allowing the gas stream from the primary sprayabsorption section to enter the secondary spray absorption section,where the gas stream may be in countercurrent contact with a secondspray absorption liquid.

The process may include feeding the liquid stream from the bottom of theprimary spray absorption section and the liquid stream from the bottomof the secondary spray absorption section as a reflux liquidrespectively into the ammonia-mixing chamber and the oxidation chamber,or combining the two streams and then separately feeding the combinedliquid stream into the ammonia-mixing chamber and the oxidation chamber.

The process may include feeding an oxygen-containing gas into theoxidation chamber, and feeding an ammonia absorbent into theammonia-mixing chamber, which is in fluid communication with theoxidation chamber.

The process may include feeding at least part of the liquid stream takenout from the lower part of the oxidation chamber as the second sprayabsorption liquid into the secondary spray absorption section, andoptionally, feeding at least part of the liquid stream taken out fromthe lower part of the oxidation chamber into a subsequent unit torecover ammonium sulfate.

The process may include feeding the liquid stream taken out from thelower part of the ammonia-mixing chamber as the first spray absorptionliquid into the primary spray absorption section.

The process may include venting the gas stream from the upper part ofthe secondary spray absorption section after removing the droplets.

The process may include further removal of fine particulate matters.

The sulfur dioxide-containing gas to be treated may be any sulfurdioxide-containing gas including those produced in any industrialproduction process. Examples of the sulfur dioxide-containing gas to betreated may include flue gas produced by coal combustion and flue gasproduced in a fluidized-bed catalytic cracking process.

Ammonia may be used as an absorbent to remove sulfur oxides in the gasstream. The ammonia may be in the form of liquid ammonia, gaseousammonia, aqueous ammonia or any combination of the aforementioned.

The oxygen-containing gas may be, for example, oxygen, air,oxygen-enriched air, oxygen-poor air, or the like.

In the oxidation section, the oxidation chamber and the ammonia-mixingchamber may be in fluid communication with each other.

In some embodiments, the ammonia absorbent is only introduced into theammonia-mixing chamber. In this way, the oxidation rates and the pH ofthe materials in the oxidation chamber and the ammonia-mixing chambercan be controlled separately.

The modality of adding the ammonia absorbent is not particularlylimited. In some embodiments, the ammonia absorbent may be addeddirectly to the liquid stream using a tubular distributor, a microporousdistributor, a static mixer, or the like. The ammonia absorbent may befirst mixed with a gas stream, e.g. air, and then the mixed gas streamis added directly to, for example, the ammonia-mixing chamber, or addedto the liquid stream, for example, to the liquid stream of theammonia-mixing chamber, using for example, a tubular distributor, amicroporous distributor, a static mixer, or the like. In the case wherethe ammonia absorbent such as liquid ammonia is mixed with the gasstream, the amount of the gas stream is not particularly limited. Theamount is such that the volume ratio of the gaseous ammonia after liquidammonia gasification to the gas stream may be 1:0.03-1:0.2. The volumeratio of the gaseous ammonia after liquid ammonia gasification to thegas stream may be 1:0.03-1:0.1.

There may be two distinct absorption-oxidation cycles. One may be theliquid stream circulation between the secondary spray absorption sectionand the oxidation chamber. The other may be the liquid streamcirculation between the primary spray absorption section and theammonia-mixing chamber. There may be some flow between the twocirculations. This may be via fluid communication between the oxidationchamber and the ammonia-mixing chamber. In addition, the pipelinestransporting circulating spray absorption liquids from the oxidationchamber and the ammonia-mixing chamber may be independent of each other.These pipelines may be in communication with each other via valvesbetween the two. These valves may be arranged to allow adjustment of theamounts and/or pH of the liquids entering the primary spray absorptionsection and the secondary spray absorption section. In addition, thereflux liquid from the primary spray absorption section and the refluxliquid from the secondary spray absorption section may be fed to theammonia-mixing chamber and the oxidation chamber respectively, or may becombined, then part of the combined reflux liquid is fed to theammonia-mixing chamber, and the other part may be fed to the oxidationchamber. In some embodiments, based on the total amount of the refluxliquids from the primary spray absorption section and the secondaryspray absorption section, 30% volume-85% volume of the reflux liquid mayenter the ammonia-mixing chamber, and the remaining reflux liquid mayenter the oxidation chamber.

In some embodiments, the spray liquid from the bottom of the primaryspray absorption section and the spray liquid from the bottom of thesecondary spray absorption section may be combined and refluxed, whereinabout 60% volume to about 70% volume, (e.g. 65% volume), of the combinedreflux liquid may enter the ammonia-mixing chamber, where the refluxliquid may be combined with the ammonia absorbent to adjust the pHvalue, and the remaining part of the combined reflux liquid may enterthe oxidation chamber.

In some embodiments, liquid ammonia may be used as the ammoniaabsorbent, wherein part of the liquid ammonia (e.g. about 55 mol% basedon the total ammonia added to the ammonia-mixing chamber). Part of theammonia may enter the reflux liquid in the ammonia-mixing chamber. Theammonia may enter uniformly, for example by using a microporousdistributor or other types of distributors. The other part of theammonia (e.g. about 45 mol% based on the total ammonia added to theammonia-mixing chamber) may be mixed with an oxygen-containing gas, e.g.air, and then may be added to the ammonia-mixing chamber. The volume ofthe oxygen-containing gas, e.g. air, may be about 3% about 10%, e.g.about 5%, of the volume of gaseous ammonia after liquid ammoniagasification.

Mainly by regulating the amount of the ammonia absorbent introduced intothe ammonia-mixing chamber and regulating the relative amount of the twoadsorption-oxidation cycles, it may be possible to control the pH of thecirculating liquids at the outlet of the ammonia-mixing chamber and atthe outlet of the oxidation chamber and to control respective oxidationrates in the oxidation chamber and the ammonia-mixing chamber. In someembodiments, the pH of the circulating liquid at the outlet of theammonia-mixing chamber may be in a range of 4.6-8.0. The pH may be in arange of 5.6-6.4. The oxidation rate in the ammonia-mixing chamber maybe in a range of 93%-99.5%. The oxidation rate may be in a range of97.5%-99%. The pH of the circulating liquid at the outlet of theoxidation chamber may be in a range of 4.0-6.8. The pH of thecirculating liquid may be in a range of 4.5-5.9. The oxidation rate inthe oxidation chamber may be not less than 98.5%. The oxidation rate maybe 98.5%-99.5%.

Optionally, in the apparatus and methods, an ammonia absorbent may alsobe added in at least one of the oxidation chamber, the coolingconcentration section, the primary spray absorption section and thesecondary spray absorption section to control the pH of the material ineach section. The pH in the cooling concentration section may becontrolled in a range of 2.5-5.5. The pH may be controlled in a range of3-3.5.

FIGS. 1, 2, and 3, illustrate embodiments. A system for treating gasincludes an absorption tower 1, an oxidation chamber 2, a coolingconcentration section 3, an aqueous ammonia source 4, a liquid ammoniasource 5, an ammonia-mixing chamber 6, an air source 7, a primary sprayabsorption section 8, a secondary spray absorption section 9, a gas cap10, a primary spray absorption circulating pump 11, and a secondaryspray absorption circulating pump 12.

A gas stream to be treated, (including, for example, flue gas such asthat produced in coal-fired boilers), may enter a cooling concentrationsection 3, via entrance 18. Within the cooling concentration section 3,the gas stream may be washed and cooled using a circulating washingliquid in the cooling concentration section while concentrating thecirculating washing liquid in the cooling concentration section usingthe heat in the flue gas. As shown in FIG. 1, an ammonia absorbent 4(including for example aqueous ammonia) may also be introduced into thegas stream in the cooling concentration section 3. The cooled gas streammay enter (including for example through a gas cap) a primary sprayabsorption section 8 upward, where the gas stream may be incountercurrent contact with a first spray liquid sprayed from the upperpart of the primary spray absorption section 8. This may absorb at leastpart of the sulfur oxides in the gas stream into the spray liquid andreduces the sulfur oxide content in the gas stream accordingly. Thecontacted first spray fluid may be collected at the bottom of theprimary spray absorption section 8, and may be taken out as the refluxliquid entering an oxidation chamber 2 and an ammonia-mixing chamber 6.

The gas stream primarily absorbed in primary spray absorption section 8may enter (including for example through a gas cap) a secondary sprayabsorption section 9 upward, where the gas stream may be incountercurrent contact with a second spray liquid entering through asprayer from the upper part of secondary spray absorption section 9, soas to further reduce the sulfur oxide content in the gas stream andpossibly reduce the amount of entrained ammonia. The contacted secondspray fluid is collected at the bottom of secondary spray absorptionsection 9, and may be taken out as reflux liquid entering oxidationchamber 2 and ammonia-mixing chamber 6. The gas stream further treatedin secondary spray absorption section 9 may be vented after removing thedroplets, or vented after further treatment through a subsequentoptional section for removal of fine particulate matters.

The reflux liquid from secondary spray absorption section 9 or part ofthe combined reflux liquid from primary spray absorption section 8 andsecondary spray absorption section 9 may enter oxidation chamber 2, andmay be mixed with an oxygen-containing gas, (including for example air7), therein, so that at least part of ammonium sulfite or ammoniumbisulfite in the reflux liquid may be oxidized to ammonium sulfate. Partof the liquid phase in the lower part of oxidation chamber 2 may betaken out through pipeline or conduit 13. At least part of the liquidstream taken out may be fed to the upper part of secondary sprayabsorption section 9 via a circulating pump 12 as the spray absorptionliquid, and optionally, at least part of the liquid stream taken out maybe fed to a downstream unit for treatment to recover ammonium sulfate.

Ammonia-mixing chamber 6 may be in fluid communication with oxidationchamber 2 through openings 15 in the upper part and side thereof,allowing material exchange between the two chambers. At least part ofthe reflux liquid from the bottom of primary spray absorption section 8or at least part of the combined reflux liquid from a port at the bottomof primary spray absorption section 8 and the bottom of secondary sprayabsorption section 9 may enter ammonia-mixing chamber 6 from the upperpart 16, and may be combined with an ammonia absorbent 5 (e.g. liquidammonia) (including for example via a microporous distributor). The restof the ammonia absorbent 5 (including for example liquid ammonia) may bemixed with air 7 and may be added to the ammonia-mixing chamber 6. Partof the liquid may be taken out from a port at the lower part of theammonia-mixing chamber 6 through pipeline or conduit 14, and may be fedto a port at the upper part of primary spray absorption section 8through circulating pump 11 as the spray absorption liquid.

Communication channel 17 may be provided between pipelines 13 and 14,and may allow adjustment of the amounts and pH values of the sprayliquids entering primary spray absorption section 8 and secondary sprayabsorption section 9. In some embodiments, an ammonia absorbent isintroduced into ammonia-mixing chamber 6. In some embodiments, anammonia absorbent is introduced in cooling concentration section 3. Insome embodiments, an ammonia absorbent is introduced in one or more ofprimary spray absorption section 8, the secondary spray absorptionsection 9, and a section for removing fine particulate matters.Different introduction site for the ammonia absorbent facilitates betterregulation and control over the composition and pH of the various liquidstreams.

In some embodiments, the ammonia-based desulfurization apparatus mayinclude primary spray absorption section 8. Primary spray absorptionsection 8 may be configured to allow countercurrent contact between afirst spray liquid sprayed from the upper part thereof and a gas streamentering from below. Primary spray absorption section 8 may also beconfigured for removal of the contacted first spray liquid from thelower part thereof to provide a reflux liquid. Primary spray absorptionsection 8 may also be configured to pass the preliminarily absorbed gasstream to secondary spray absorption section 9, for example, through apartition with a gas cap.

In some embodiments, the ammonia-based desulfurization apparatus mayinclude secondary spray absorption section 9. Secondary spray absorptionsection 9 may be configured to allow countercurrent contact between asecond spray liquid sprayed from the upper part thereof and a gas streamentering from primary spray absorption section 8. Secondary sprayabsorption section 9 may also be configured for removal of the contactedsecond spray liquid from the lower part thereof to provide a refluxliquid.

In some embodiments, the ammonia-based desulfurization apparatus mayinclude an oxidation section 2. Oxidation section 2 may include anoxidation chamber which may be configured to allow contact and reactionbetween oxygen-containing gas 7 and at least part of the reflux liquidfrom secondary spray absorption section 9 or part of the combined refluxliquid from primary spray absorption section 8 mixed with liquid fromsecondary spray absorption section 9. Oxidation section 2 may also beconfigured for removal of liquid phase from the lower part thereof forcirculation in secondary spray absorption section 9 or both secondaryspray absorption section 9 and primary spray absorption section 8.

In some embodiments, the ammonia-based desulfurization apparatus mayinclude ammonia-mixing chamber 6. Ammonia-mixing chamber 6 may beconfigured to be in fluid communication with oxidation chamber 2 viaopenings on its top and/or side. Ammonia-mixing chamber 6 may beconfigured to allow at least part of the reflux liquid from primaryspray absorption section 8 or part of the combined reflux liquid fromthe primary and secondary spray absorption sections 8, 9 to enter fromthe upper part thereof and mix with an ammonia absorbent. Ammonia-mixingchamber 6 may be configured for removal of a liquid stream from thelower part thereof for circulation in the primary spray absorptionsection 8 or both the secondary and primary spray absorption sections 8,9.

In some embodiments, the ammonia-based desulfurization apparatus mayinclude cooling concentration section 3. Cooling concentration section 3may be upstream of primary spray absorption section 8. Coolingconcentration section 3 may be configured to allow a gas stream to betreated, (including for example flue gas produced in coal-firedboilers), to be washed and cooled by a circulating washing liquid in thecooling concentration section while concentrating circulating washingliquid in the cooling concentration section using the heat in the gasstream. Cooling concentration section 3 may be also be configured toallow the cooled gas stream to enter the primary spray absorptionsection 8. The gas may enter primary spray absorption section 8 bypassing through a partition with a gas cap.

In some embodiments, each section of the apparatus may be positionedwithin an absorption tower. When so positioned, the volume of theoxidation chamber may be determined based on the residence time requiredfor oxidation. In some embodiments, the volume of the ammonia-mixingchamber is generally not less than the volume of fluid which passesthrough circulation pumps like 11 or 12 over a period of two minutes.

In some embodiments, oxidation chamber 2 and ammonia-mixing chamber 6 inthe oxidation section may be provided separately. For example, theoxidation chamber and the ammonia-mixing chamber may be provided by twotanks in fluid communication with each other. As another example, theoxidation chamber may be provided in an absorption tower accommodatingeach section of the apparatus, and the ammonia-mixing chamber may beprovided in the absorption tower or outside the absorption tower.

In some embodiments, the oxidation chamber and the ammonia-mixingchamber in the oxidation section may be formed by one or more than onepartition using a tank(s). Both the oxidation chamber and theammonia-mixing chamber in the oxidation section may be provided in anabsorption tower accommodating each section of the apparatus, and may beformed by a partition in the lower part of the absorption tower. In suchan embodiment, the cross-sectional area of the ammonia-mixing chamber atmost may account for 85% (e.g. no more than 60%, or no more than 50%, orno more than 40%, or is in a range of 8%-50%, or is in a range of10%-40%, or is in a range of 12%-35%) of the cross-sectional area of thetank/absorption tower.

The ammonia-mixing chamber may be provided below the control level ofthe oxidation chamber. For example, the top of the ammonia-mixingchamber may be at least 20 cm below the control level of the oxidationchamber. The top of the ammonia-mixing chamber may be 100-200 cm belowthe control level of the oxidation chamber.

In some embodiments, there may be no openings on the bottom surface ofthe ammonia-mixing chamber.

In some embodiments, one or more balance holes in fluid communicationwith the oxidation chamber may be opened on the side of theammonia-mixing chamber. The balance hole(s) may be opened in the lowerpart of the side, e.g. in the ⅛ lower part, or in the ⅙ lower part, orin the ⅕ lower part, or in the ¼ lower part, or in the ⅓ lower part ofthe side. The area of each opening may be not more than 0.25 m². Thearea may be not more than 0.1 m². The area may be not more than 0.05 m².The area may be not more than 0.01 m². The shape of the opening is notparticularly limited. For example, the opening may be a round, arectangle, a square, an oval, a hexagon, or the like. In a specificembodiment, the opening may be a square of 80×80 mm or 90×90 mm or100×100 mm. In another specific embodiment, the opening may be roundwith a diameter of 80, or 85, or 90, or 95, or 100, or 110 mm.

The number of the openings on the side can be calculated according tothe cross-sectional area required to at least reach the flow of a singlecirculating pump and the area of a single opening at a flow rate of 4m/s. In general, the number of the openings on the side enables thetotal area of the openings to be equal to or larger than thecross-sectional area required to reach the flow of a single circulatingpump at a flow rate of 4 m/s.

There may also be one or more openings on the roof of the ammonia-mixingchamber. In general, the number of the openings on the roof may be 1-3times as much as the number of the openings on the side, and the size ofthe openings on the roof may be the same as or different from the sizeof the openings on the side. The shape of the openings on the roof maybe the same as or different from the shape of the openings on the side.The balance holes on the side and top of the ammonia-mixing chambershould be generally provided away from the inlet and outlet of eachmaterial. In some embodiments, FIG. 3 schematically describes thearrangement of openings of an ammonia-mixing chamber. The arrangement ofthe openings on the side and/or top of the ammonia-mixing chamber allowsseries flow between the two circulations.

The shape of the ammonia-mixing may be determined according to itslocation and the relative ease of assembling, accessing, operating, andmaintaining the equipment. For example, in the case where the ammoniachamber is connected to the tower or tank wall, it may besemi-cylindrical; in the case where the ammonia chamber may be placed inthe middle of the tower, it may be processed into a horizontal tank; andin the case where the ammonia chamber is placed outside the tower, itmay be manufactured as a cylindrical vertical tank.

In some embodiments, as shown in FIGS. 1-3, the cross sectional area ofthe ammonia-mixing chamber 6 may be about 15% (about 30%, e.g. 18%, 20%,22% or 25%) of the cross sectional area of absorption tower 1. Theheight of ammonia-mixing chamber 6 may be about 30 (about 42%, e.g. 35%,38% or 40%) of the height of the oxidation section. The overallammonia-mixing chamber 6 may be below the control level within oxidationchamber 2 (e.g. at least about 50 cm below the control level, e.g. 60cm, 80 cm, 100 cm or 150 cm below the control level). The volume ofammonia-mixing chamber 6 may be about 15-40 m³ (e.g. 18, 22 or 26m^(3).)

The volume of oxidation chamber 2 may be about 150-400 m³ (e.g. 180, 220or 260m³). The volume ratio of ammonia-mixing chamber 6 to oxidationchamber 2 may be about 1:10. Ammonia-mixing chamber 6 may have between 5to 15 balance holes 15 in the lower part of the side (e.g. in the ¼ or ⅕or ⅙ of the lower part). Ammonia- mixing chamber 6 may have between10-30 (e.g. 20) balance holes 15 on the roof. The size of each hole maybe 80×80 mm. The balance holes are located away from the inlet of thereflux liquid and ammonia intake.

The reflux liquid from primary spray absorption section 8 and the refluxliquid from secondary spray absorption section 9 may be combined. 60-70%of the volume (e.g. 65% volume) of the total reflux liquid may enterammonia-mixing chamber 6 and may be mixed with liquid ammonia 5. Theremaining portion of the reflux liquid may enter oxidation chamber 2.Based on the total amount of liquid ammonia fed to ammonia-mixingchamber 6, for example, about 55% of liquid ammonia 5 may be addeddirectly to ammonia-mixing chamber 6 (including for example through amicroporous distributor). The remaining 45% of liquid ammonia 5 may bemixed with air 7 and then fed to ammonia-mixing chamber 6. The volume ofair 7 may be about 5%-10% of the volume of gaseous ammonia present afterliquid ammonia gasification. Valves may be set on each pipeline orconduit from/to oxidation chamber 2 and ammonia-mixing chamber 6 asappropriate, so as to allow adjustment of the flows of materials from/tothe two chambers, and to allow adjustment of the compositions of theliquid streams from/to the two chambers.

EXAMPLES Example 1

An ammonia-based desulfurization of the flue gas from a coal combustionprocess was carried out with an embodiment of the apparatus and methods,such as that illustrated in FIGS. 1-3, except that an oxidation chamberand an ammonia-mixing chamber were provided by two tanks outside anabsorption tower. The apparatus included a DN500 communication pipelocated in the middle part of the two tanks. A first liquid wascirculated from an outlet in a lower part of the ammonia-mixing chamberinto an upper part of a primary spray absorption section. A secondcirculating liquid flowed from an outlet in a lower part of theoxidation chamber into an upper part of a secondary spray absorptionsection. A first reflux liquid was formed from the primary sprayabsorption section and a second reflux liquid was formed from thesecondary spray absorption section. The first and second reflux liquidsconverged at a gas-liquid separator between a cooling concentrationsection and the primary spray absorption section to form a mixed refluxliquid. The rate of liquid flow was 2700 m³/h, wherein 60% volume of thereflux liquid entered the ammonia-mixing chamber, and 40% volume of themixed reflux liquid entered the oxidation chamber. Liquid ammonia wasadded to the ammonia-mixing chamber uniformly and gently at a flow rateof 204 kg/h through a microporous distributor. The remaining liquidammonia was added to air at a rate of 300 kg/h through a distributor.The air volume was 10% of the volume of gaseous ammonia after liquidammonia gasification. The mixed gas was fed to the ammonia-mixingchamber. The volume of the ammonia-mixing chamber was 27 m³; the volumeof the oxidation chamber was 200 m³. No stream was fed to downstreamunits to recover ammonium sulfate.

The flow rate of the original flue gas was 600,000 Nm³/h, itstemperature was 145° C., its SO₂ concentration was 1600 mg/Nm³, and theconcentration of total particulate matter was 21.3 mg/Nm³. The pH of thecirculating liquid at the outlet in the lower part of the ammonia-mixingchamber was 6.1, and the oxidation rate in the ammonia-mixing chamberwas 98%. The pH of the circulating liquid at the outlet in the lowerpart of the oxidation chamber was 5.3, and the oxidation rate in theoxidation chamber was 99.5%. The gas temperature at the outlet of thecooling concentration section was 51.4° C.

After undergoing the ammonia-based desulfurization process, the SO₂content in the resulting cleaned flue gas from the secondary sprayabsorption section was 17.3 mg/Nm³, the content of total particulatematters (including aerosols) was 1.8 mg/Nm³, and the amount of entrainedammonia was 0.35mg/Nm³.

Example 2

The procedure of Example 1 was repeated, except that the oxidationchamber and the ammonia-mixing chamber were provided within a commontank with a diameter of 5.5 m, the cross-sectional area of theammonia-mixing chamber was 18% of the cross-sectional area of the tank,and the top of the ammonia-mixing chamber was 1 m lower than the liquidlevel in the oxidation chamber. 13 balance holes were disposed in alower part on the side of the ammonia-mixing chamber, 22 balance holeswere disposed on the roof. The size of each hole was 80×80 mm. Thebalance holes were provided away from the outlet of the circulatingliquid and away from the ammonia intake. The volume of theammonia-mixing chamber, with a semi-cylindrical shape, was 27 m³. Thevolume of the oxidation chamber was 220 m³. A first spray liquid fromthe primary spray absorption section and a second spray liquid from thesecondary spray absorption section were combined into a reflux liquid.70% of this combined reflux liquid was combined with 20% aqueous ammoniaat a rate of 2522 kg/h and then entered the ammonia-mixing chamber,while the remaining reflux liquid entered the oxidation chamber.

The pH of the circulating liquid taken out from the ammonia-mixingchamber was 6.3, and the oxidation rate in the ammonia-mixing chamberwas 98.6%. The pH of the circulating liquid taken out from the oxidationchamber was 5.4, and the oxidation rate in the oxidation chamber was99.7%.

After undergoing the ammonia-based desulfurization process, the SO₂content in the cleaned flue gas was 16.3 mg/Nm³, the content of totalparticulate matters (including aerosols) was 2.1 mg/Nm³ and the amountof entrained ammonia was 0.42 mg/Nm³.

Example 3

The procedure was carried out using the apparatus of Example 1, exceptthat the oxidation chamber and the ammonia-mixing chamber were providedin a common tank with a diameter of 6 m. The cross-sectional area of theammonia-mixing chamber was 20% of the cross-sectional area of the tank.The top of the ammonia-mixing chamber was 1.5 m lower than the liquidlevel in the oxidation chamber. Eight balance holes were disposed in thelower part on the side of the ammonia-mixing chamber. Thirteen balanceholes were disposed on the roof, the size of each single hole was100×100 mm. The balance holes were provided away from the outlet of thecirculating liquid and away from the ammonia intake. The volume of theammonia-mixing chamber was 25 m³. The ammonia-mixing chamber was locatedin the middle of the tank, and was disposed horizontally in the tank.The volume of the oxidation chamber was 228 m³. The first spray liquidfrom the primary spray absorption section and the second spray liquidfrom the secondary spray absorption section were not combined. Instead,the two spray liquids were fed to the ammonia-mixing chamber and theoxidation chamber respectively. The flow rate of the sprayed liquid backto the ammonia-mixing chamber was 1700 m³/h. The flow rate of the secondsprayed liquid back to the oxidation chamber was 600 m³/h. 20% aqueousammonia used as an absorbent was added to the sprayed liquid enteringthe ammonia-mixing chamber at a flow rate of 5432 kg/h, and was added tothe sprayed liquid entering the oxidation chamber at a flow rate of 1316kg/h.

The flow rate of the original flue gas was 300000 Nm³/h, its temperaturewas 145° C., the SO₂ concentration was 8500 mg/Nm³, and theconcentration of total particulate matters was 28.5 mg/Nm³.

The pH of the circulating liquid taken out from the ammonia-mixingchamber was 6.5, and the oxidation rate in the ammonia-mixing chamberwas 96.8%. The pH of the circulating liquid taken out from the oxidationchamber was 5.3, and the oxidation rate in the oxidation chamber was99%.

After undergoing the ammonia-based desulfurization process, the SO₂content in the cleaned flue gas was 31.4 mg/Nm³, the content of totalparticulate matters (including aerosols) was 2.8 mg/Nm³, and the amountof entrained ammonia was 0.7 mg/Nm³.

Example 4

The experiment of Example 3 was repeated, except that ammonification indifferent chambers was not employed. Instead the ammonia-mixing chamberand the oxidation chamber were combined into one. The first spray liquidfrom the primary spray absorption section and the second spray liquidfrom the secondary spray absorption section were combined at a rate of2300 m³/h and then entered the oxidation chamber, before which 20%aqueous ammonia was added at a rate of 6770 kg/h. After oxidation, thespray liquids returned to the primary and secondary spray absorptionsections for absorption. The pH of the oxidized circulating liquid was5.9 and the oxidation rate was 98.3%.

After passing through the apparatus, the SO₂ content was 67 mg/Nm³, thecontent of total particulate matters (including aerosols) was 12 mg/Nm³,the amount of entrained ammonia was 2.7 mg/Nm³, and consumption of 20%aqueous ammonia was increased by 22 kg/h compared to the consumptionthat occurred in Example 3. These results indicate inferior performancecompared to that achieved by Example 3.

The detection methods of some indicators and main instruments in theexamples are shown in Table 1 below

TABLE 1 Detection methods of some indexes and main instruments Standardnames Instrument Monitoring and numbers of names Instrument S/N itemsanalysis methods and models Nos. 1 Flue dust Determination of Laoying8042448, particulates and sampling 3012H 08244496 methods of gaseousflue dust 18360886 pollutants emitted from sampler and exhaust gas ofstationary Electronic 1119051201 source (Chinese balances EnvironmentalStandard BS224S and GB/T16157-1996) AB204-S 2 SO₂ Determination ofsulphur Testo 350 10# and 1# dioxide from exhausted flue gas gas ofstationary source analyzer Fixed-potential electrolysis (ChineseEnvironmental Standard HJ/T 57-2000) 4 Ammonia Air and exhaust gas-Laoying 02085809 Determination of 3072H and ammonia- 722 spectro-2c5BP363 Nessler's reagent photometer spectrophotometry (ChineseEnvironmental Standard HJ 533-2009) 5 Flue gas Specification and testTesto 350 10# and 1# oxygen procedures for flue gas content continuousemission analyzer monitoring systems of flue gas emitted from stationarysources- Electrochemical process (Appendix B) (Chinese EnvironmentalStandard HJ/T 76-2007) 6 Flue gas Determination of TES-1310 —temperature particulates and sampling methods of gaseous pollutantsemitted from exhaust gas of stationary source-Platinum resistance method(Chinese Environmental Standard GB/T16157-1996) 7 Flue gas Specificationand test Laoying 8042448 humidity procedures for 3012H and continuousemission flue dust 08244496 monitoring systems of sampler flue gasemitted from stationary sources (Appendix B) (Chinese EnvironmentalStandard HJ/T 76-2007)

The present disclosure illustrates principles of the invention and isnot intended to limit the invention to the particular embodimentsillustrated. All patents, patent applications, scientific papers, andany other referenced materials mentioned herein are incorporated byreference in their entirety. The principles of the invention encompassany possible combination of some or all of the various embodimentsmentioned herein, described herein and/or incorporated herein. Theprinciples of the invention encompass any possible combination that alsospecifically excludes any one or some of the various embodimentsmentioned herein, described herein and/or incorporated herein.

All ranges and parameters disclosed herein are understood to encompassany and all subranges subsumed therein, and every number between theendpoints. For example, a stated range of “1 to 10” should be consideredto include any and all subranges between (and inclusive of) the minimumvalue of 1 and the maximum value of 10; that is, all subranges beginningwith a minimum value of 1 or more (e.g. 1 to 6.1), and ending with amaximum value of 10 or less (e.g. 2.3 to 9.4, 3 to 8, 4 to 7), and toeach number 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 contained within therange. All percentages, ratios and proportions herein are by weightunless otherwise specified.

Thus, apparatus and methods for using ammonia to remove sulfur dioxidefrom exhaust gases have been provided. Persons skilled in the art willappreciate that the present invention can be practiced by other than thedescribed embodiments, which are presented for purposes of illustrationrather than of limitation. The present invention is limited only by theclaims that follow.

What is claimed is:
 1. A method of ammonia-based oxidativedesulfurization comprising; directing a current of sulfur dioxidecontaining gas through a vessel; mixing, in an ammonia-mixing chamber, aliquid and an ammonia source to produce a first ammonia-containingliquid that has a first pH; contacting, in an oxidation chamber, anoxygen-containing gas with a second ammonia-containing liquid that has asecond pH that is lower than the first pH; spraying, via a first sprayerassembly, the first ammonia-containing liquid in the vessel against thecurrent; after the spraying the first ammonia-containing liquid,recirculating the first ammonia-containing liquid to the ammonia-mixingchamber; spraying via a second sprayer assembly, the secondammonia-containing liquid in the vessel against the current; after thespraying the second ammonia-containing liquid, recirculating the secondammonia-containing liquid to the oxidation chamber; and fluidicallycommunicating the ammonia-mixing chamber and the oxidation chamber witha primary absorption section of the vessel upstream from the firstsprayer assembly via a conduit having a first end and a second end, thefirst end configured to be joined to the primary spray absorptionsection, the second being bifurcated and configured to be joined to: theoxidation chamber; and the ammonia-mixing chamber.
 2. The method ofclaim 1 further comprising, before the spraying the firstammonia-containing liquid in the vessel against the current, cooling thecurrent by contacting it with recirculated sprayed ammonia-containingliquid.
 3. The method of claim 1 further comprising, before the sprayingthe first ammonia-containing liquid in the vessel against the current,cooling the current by contacting the current with ammonium sulfateslurry.
 4. The method of claim 1 further comprising releasing the gascurrent from the vessel; wherein: in the directing, the sulfur dioxidecontaining gas has: an SO₂ concentration not more than 30000 mg/Nm³; anda total particulate matter concentration not more than 30 mg/Nm³; andthe releasing includes: releasing an exhaust gas having an SO₂concentration no more than 35 mg/Nm³; and a total dust, includingaerosols, content no more than 5 mg/Nm³.
 5. The method of claim 1further comprising receiving the gas current from a coal combustionprocess.
 6. The method of claim 1 further comprising receiving the gascurrent from a fluid catalytic cracking process.
 7. The method of claim1 wherein the ammonia source comprises anhydrous ammonia.
 8. The methodof claim 1 wherein the ammonia source comprises gaseous ammonia.
 9. Themethod of claim 1 wherein the ammonia source comprises aqueous ammonia.10. The method of claim 1 further comprising, after the spraying, thefirst and second ammonia-containing liquids, mixing the first and secondammonia-containing liquids to form a mixed reflux liquid.
 11. The methodof claim 10 further comprising circulating the reflux liquid into theoxidation chamber.
 12. The method of claim 10 further comprising passingbetween 30% and 85% of the reflux liquid into the ammonia-mixingchamber.
 13. The method of claim 10 further comprising circulatingbetween 70% and 15% of the reflux liquid into the oxidation chamber. 14.The method of claim 10 further comprising contacting anhydrous ammoniawith the reflux liquid via a microporous distributor and adding theresulting mixture into the ammonia-mixing chamber.
 15. The method ofclaim 1 wherein the oxygen-containing gas is pure molecular oxygen. 16.The method of claim 1 wherein the oxygen-containing gas is oxygen-poorair.
 17. The method of claim 1 wherein the oxygen-containing gas isoxygen-enriched air.
 18. The method of claim 1 further comprising, priorto the mixing of the liquid and the ammonia source, mixing the ammoniasource with the oxygen-containing gas.
 19. The method of claim 1 whereinthe pH of the second ammonia-containing liquid is in the range 4.0 to6.8.
 20. The method of claim 1 further comprising releasing the gascurrent from the vessel, wherein the released gas current has anentrained ammonia amount no more than 3 mg/Nm³.
 21. The method of claim1 wherein the ammonia-mixing chamber is disposed separately from theoxidation chamber.
 22. The method of claim 1 wherein the ammonia-mixingchamber is disposed at least partly within the oxidation chamber. 23.The method of claim 1 wherein the spraying the first ammonia-containingliquid in the vessel against the current occurs before the spraying thesecond ammonia-containing liquid in the vessel against the current. 24.An apparatus for removing sulfur from a gas stream, the apparatuscomprising: a first sprayer circuit configured to spray a first liquidcountercurrent to the gas stream, the first sprayer circuit including: afirst sprayer assembly; and an ammonia-mixing chamber including: anammonia input port; a first-liquid return port configured to receivefirst liquid after the first liquid is sprayed; and a first-liquidsupply port configured to supply first liquid to the first sprayerassembly, the ammonia-mixing chamber defining a balance hole that placesmaterial from inside the ammonia-mixing box in diffusive communicationwith material from outside of the ammonia-mixing box; and a secondsprayer circuit configured to spray a second liquid countercurrent tothe gas stream, the second sprayer circuit including: a second sprayerassembly downstream, relative to the gas stream, from the first sprayerassembly; and an oxidation chamber having: a gas input configured forcontacting an oxygen-containing gas with an ammonia-containing liquid inthe oxidation chamber; a second-liquid return port configured to receivesecond liquid after the second liquid is sprayed; and a second-liquidsupply port configured to supply second liquid to the second sprayerassembly; wherein, after the first and second liquids are sprayed, thefirst and second liquids are mixed to form a mixed reflux liquid. 25.The apparatus of claim 24 further comprising a cooling chamber in whichthe gas stream is cooled, before spraying the first liquidcountercurrent to the gas stream, by contacting the gas stream withrecirculated sprayed ammonia-containing liquid.
 26. The apparatus ofclaim 24 further comprising a gas cap configured to transfer the gasstream from the first sprayer assembly to the second sprayer assembly.27. The apparatus of claim 24 further comprising a sealable valveconfigured to adjust fluid communication between a first conduitcarrying the first liquid from the first-liquid supply port and a secondconduit carrying the second liquid from the second-liquid supply port.28. The apparatus of claim 24 wherein the ammonia-mixing chamber has avolume no less than a volume of the first liquid that is supplied to afirst sprayer array over a period of two minutes.
 29. The apparatus ofclaim 24 wherein the ammonia-mixing chamber is disposed at least partlywithin the oxidation chamber.
 30. The apparatus of claim 24 wherein: theammonia-mixing chamber has a first cross-sectional area; the oxidationchamber has a second cross-sectional area; and the secondcross-sectional area is larger than the first cross-sectional area.